The usual one-electron populations in atomic orbitals of closed shell systems are split into unpaired and paired at the (spin-dependent) second-order reduced density matrix level. The unpaired electron in an orbital is defined as the “simultaneous occurrence of an electron and an electron hole of opposite spins in the same spatial orbital,” which for simplicity is called “electropon.” The electropon population in a given orbital reveals whether and to what degree the Coulomb correlations, and hence, the chemical bonding between this orbital and the remaining orbitals of the system are globally favorable or unfavorable. The interaction of two electropons in two target orbitals reveals the quality (favorable or unfavorable) and the strength of the covalent bonding between these orbitals; this establish a bridge between the notion of “unpaired electrons” and the traditional covalent structure of valence-bond (VB) theory. Favorable/unfavorable bonding between two orbitals is characterized by the positive/negative (Coulomb) correlation of two electropons of opposite spins, or alternatively, by the negative/positive (Fermi) correlation of two parallel spin electropons. A spin-free index is defined, and the relationship between the electropon viewpoint for chemical bonding and the well-known two-electron Coulomb and Fermi correlations is established. Benchmark calculations are achieved for ethylene, hexatriene, benzene, pyrrole, methylamine, and ammonia molecules on the basis of physically meaningful natural orbitals. The results, obtained in the framework of both orthogonal and nonorthogonal population analysis methods, provide the same conceptual pictures, which are in very good agreement with elementary chemical knowledge and VB theory. © 2013 Wiley Periodicals, Inc.